Azodyestuffs



Patented Dec. 5, 1933 UNITED STATES PATENT OFFICE AZODYESTUFFS Ernst Fellnfier, Leverkusen-on-the-Rhine, Germanyya'ssignor to General Aniline Works, Inc., New York, N. Y., a corporation of Delaware No Drawing. Application September 4, 1930.,

Serial No. 79,793, and in Germany September 7 Claims (Cl. 2(i071) Y The present invention relates to azodyestuffs and to the products dyed therewith.

The process of manufacture in accordance with the invention is by tetra'zotizing a benzidine sulfonicor -carboxylic' acid or a derivative thereof, coupling with two molecules of afnoiddle component capable ofv 'further fdiazoti'zation, again diazotizingand coupling with one molecule of a naphthalene-sulfonic acid of the probable formula: s I

HOaS': I

wherein X stands forhydrogen or the sulf onic acid. group, Y stands for hydrogen or for alkyl which may be substituted by; a hydroxyor an amino-group, or forbenzylwhich'ma'y be substituted by a sulfo-, carboxylic acid,fhydroXy-- or an amino-group, and with one molecule of a naphthalene sulfonic acid of the probable" formula form dark colored. alkali metal salts, Which'are soluble in water, dyeing silk generally bluish black to black shades of goo fastn'ess -t'o water, They probably correspond to the general formula: I

" wherein R represents a benz idine residue being substituted by sulfonic acidor carboxylic acidgroups, R1 and R2 stand for aromatic radicals of the benzene series, X stands for hydrogen or a sulfonic acid group, Y stands for hydrogen or alkyl which maybe substituted by a hydroxyoranamino-group, or for benzyl which may be substituted by a su1fo-, carboxylic acifl hydroxy- .or an amino group, Z stands for hydrogen or alkyl which maybe substituted by a hydrxy or an amino-group, but only one of the symbols Y and 'Z being hydrogen, and Q stands for hydrogen or for the sulfonic acid group.

The invention is illustrated by the following examples, without being limited thereto:

Example 1.-34,4 parts by weight of benzidine- :o-disulfonic acid are tetrazotized at 10 C. with 13,8 parts byweight of sodium nitriteand hydrochloric acid, and to this mixture there is added a solution of 27,4 parts by weight of cresidine and hydrochloric acid, the acid reaction of the final mixture to congo paper being removed by the addition of sodium acetate. When the coupling is complete the isolated di'aminodisazo compound is tetrazotized with 13,-8 p'arts by weight of sodium nitrite and hydrochloric acid and stirred for sever'al hours at'or'dinary" empe'rature. The soda,

alkaline seiution cf 31,9 parts" by weight or 2.8- aminonaphtho1-3.6-disii- 7 ii: acid and 29,5 parts by weight or bLItyI-Z-ahiino8 haphthbl-6-sulfonic acid is added to the solution and the dyestuif produced having the following formula:

N=N V NR2 QHQO HO 3 SOaH N N N SOzH SOIH

omo- 0H N Nil-0411a HOaS is isolated in the customary manner and dyes silk deep black shades.

Example 2.The diaminodisazo compound obtainable in accordance with Example 1 is tetrazotized with 13,8 parts by weight of sodium nitrite and hydrochloric acid and stirred for several hours at ordinary temperature. The tetrazo compound is coupled with the soda alkaline solution of 31,9 parts by weight of 2.8-aminonaphthol-3.6- disulfonic acid and 28,3 parts by weight of 2- hydroxyethyl-amino-i;-naphthol-6-sulfonic acid and the dyestuff thus produced having the following formula:

is isolated in the customary manner and dyes silk in deep black shades.

Example 3.--The diaminodisazo compound obtainable in accordance with Example 1 is tetrazotized with 13,8 parts by weight of sodium nitrite and hydrochloric acid and coupled with the soda alkaline solution of 72,4 parts by weight of 2- aminoethylamino-S-naphthol-3.6-disulfonic acid.

The dyestufi thus produced having the following formula:

N NHCH:CHa-NH3 Hols som CH5 i SOaH SOaH

s CH3 V N N NHCH2 -CH2NH2 H03 SO3H is isolated in the customary manner and dyes silk in deep greenish black shades. V

Example 4.The diaminodisazo compound obtainable in accordance with Example l is tetra zotized with 13.8 parts by weight of sodium nitrite and hydrochloric acid and coupled with 31.9 parts by weight of 2.8-aminonaphthol-3.6- disulfonic acid and 32.9 parts by weight of 2- benzyl-amino-8-naphthol-6-sulfonic acid in soda alkaline solution. The dyestufi thus produced having the following formula:

' also is isolated irifirle mannefafianybs silk black shades.

I claim: x I i 1. Azodye'stufis'of the generalforfnulaz 5 5 i -1 wherein R represents a benzidine residue being V droxyo an -ero lnbutm y-'o eio rtba ,1 sym ols-land .Zi ein hydr a d Q sta s "for hydrogen or for a sulfonic acid group, being in the dry state dark grey to black powders, "soluble in strong sulfuric acid with dark blue to bluish black colorations. 2. Azodyestuffs of the general formula: e.

wherein R1 and R2 stand for aromatic radicals of the benzene series,'X stand for hydrogen or a sulfonic acid group, Y stands for hydrogen or alkyl which may be substituted by a hydroxyor an amino-group, or for benzyl which may be substituted by a sulfonic acid-, carboxylic acid-, hydroxyor an amino-group, Z stands for hydrogen or alkylwhich may be substituted by a hy- 'droxyor an amino-group but only one of the symbols Y and Z being hydrogen, and Q stands for hydrogen. or for a sultonic acid group, being in the dry state dark grey to black powders, soluble in strong sulfuric acid with dark blue to bluish black colorations.

aoidg carboxylic acid hydroxyor an amino'- wherein R1.andR standforb erizene nuclei, X

stands for hydrogen or a sulfonic acid group, Y 10.5,? stands for hydrogen, or alkylwhich may be substituted by a hydroxy or an amino-group, or for benzyl which may be su bstitute d by asulfonic group, 2- stands for hydrogen or alkyl hi hQmay 11 be substituted'by a hydroxyor an arriino g'rou'p, but only one of the symbols Y and Z being hydrogen, and Q stands for hydrogen or for a sulfonic acid group, beingiri the dry;state dark grey to black powders, soluble in strong,, sulfuric acid 11%? with dark bluetoblui sh blackcolo'rations.

4. Azodyestuffs of the general'formula:

wherein R1 and R2 stand for benzene nuclei and 2 Z stands for alkyl which may be substituted by a hydroxyor an amino-group, being in the dry state dark grey to'black powders, soluble in strong sulfuric acid with dark blue to bluish black colorations. 150* 5. The azodyestuff of the formula.

OHaO

OHaO- OH N=N NH- 04110 Hogsbeing a dark powder and dyeing silk deep black which dyes silk black ERNST FELLNIER.

shades.

6. The azodyestufi 0f the formula:

1TI==N NHz CH30- H03 4303B:

son:

SOzH

N bk

CHaO OH N=N NH-CzEh-OH which dyes silk deep black shades.

7. The azod'yesbufi of the formula:

HOaS

NH-CHr-CsHd 

